CN201307967Y - Double-sided flexible copper-clad plate - Google Patents
Double-sided flexible copper-clad plate Download PDFInfo
- Publication number
- CN201307967Y CN201307967Y CNU2008202142149U CN200820214214U CN201307967Y CN 201307967 Y CN201307967 Y CN 201307967Y CN U2008202142149 U CNU2008202142149 U CN U2008202142149U CN 200820214214 U CN200820214214 U CN 200820214214U CN 201307967 Y CN201307967 Y CN 201307967Y
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- copper foil
- copper
- double side
- side flexible
- flexible copper
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Abstract
The utility model relates to a double-sided flexible copper-clad plate, comprising: a first copper foil, a polyimide layer coating on the first copper foil, an adhesive layer coating on the polyimide layer and a second copper foil pressing on the adhesive layer. The double-sided flexible copper-clad plate has characteristics of ultra-thinness and no corrugation of golden fingers of a circuit board, and has excellent folding resistance, heat tolerance, fire resistance property and good processing property, and is also low in cost and convenient in mass production.
Description
Technical field
The utility model relates to a kind of double side flexible copper coated board, relates in particular to a kind of slimming double side flexible copper coated board.
Background technology
Along with the slim lightweight of electronic product, require the also slim thereupon lightweight of circuit base material.Therefore the rigidity wiring board develops into flex circuit application or rigid-flexible combined circuit board.Particularly mobile phone needs large scale display, makes clamshell phone and slide phone in vogue.In order to pursue the connection reliability of renovating hinge part and slip lid, must make the base material of circuit have more slim and higher resistance to deflection, high-dimensional stability.In addition, LCD assembles requirement, and the resilience force of line of deflection roadbed material is low, and the way of solution also is the slimming more of requirement base material.The traditional manufacture method of flexible polyimide copper clad lamination is three layers the glue type, it is to be coated with modified epoxide resin adhesive or the acrylate adhesive that last layer thickness is 6-30 μ m on the polyimide film of commercially available 12.5-50 μ m, after oven dry and Copper Foil roll-in are compound, another side at polyimide film is coated with identical adhesive again, after the oven dry again with the Copper Foil pressing, carry out hot curing then and obtain the double side flexible copper coated board that insulating substrate thickness is 24.5-110 μ m.In general the thickness of this double side flexible copper coated board is owing to be subjected to the influence of polyimide film (commercialization generally has only the product of specification such as 10,12.5,25,50 μ m) and bondline thickness, be difficult to do thinlyyer, if glue-line is thinner, the caking property of glue-line is descended, and in general bondline thickness can not be lower than 6 μ m.For slimming, present most of manufacturer develops the two-layer method flexibility coat copper plate that does not use epoxy glue or acrylate adhesive, can make thickness thinner, now the minimal thickness of commercially produced product can reach 14 μ m, it is to apply thermoplastic polyimide layer or make laminated film at the Thermocurable polyimide laminar surface, obtain double side flexible copper coated board with Copper Foil in the high temperature pressing, this is two layers of no gum base materials of so-called laminating.Because tack coat is the thermoplastic polyimide adhesive, for reaching the soldering resistance requirement, necessarily require the fusing point of thermoplastic polyimide glue-line to surpass 260 ℃, therefore need a kind of compound press of high temperature hot-rolling that surpasses more than 260 ℃.Because the compound press cost of investment of high temperature is very high, production efficiency is low, cause the overall product cost higher, on the other hand, material is at continuous compound tense, Copper Foil or polyimide film moment contact high temperature roller owing to the reason of heat expansion is easy to make material production wrinkle or ripple, finally influence the surface quality of finished product.Therefore the cost of two layers of method double sided board is much higher than the three-layer process double sided board, and apparent being difficult to controlled.At present, though two layers of method double sided board have plurality of advantages, market is under the pressure of cost pressure, and manufacturer terminal still uses the three-layer process double sided board than more options.
In order to reduce cost, improve the performance of double side flexible copper coated board simultaneously, solve the slimming problem of double side flexible copper coated board, the utility model adopts the advantage of two layers of method and three-layer process flexibility coat copper plate, comprehensive both manufacture methods, on Copper Foil, be coated with earlier the polyamic acid 8-25 μ m of the heat-resisting and high-dimensional stability of a floor height, through becoming polyimide film single face flexibility coat copper plate after the high-temperature sub amination, on the polyimides face, be coated with the adhesive of one deck 6-25 μ m again with traditional three-layer process, this adhesive can be an adhesive epoxy binder modified or acrylate adhesive or other type, adhesive can be that the fire-retardant or halogen-free flameproof of halogen is arranged, also can be not fire-retardant, then with the three-layer process combination process, at a certain temperature with the compound another side of Copper Foil, obtaining base material after the curing has the insulating substrate of one deck polyimides and one deck adhesive, gross thickness is the double side flexible copper coated board of 14-50 μ m, this process is not used the high temperature composite roll, and it is smooth therefore can to make surface quality, low-cost, the double-sided polyimide flexibility coat copper plate that the slimming combination property is outstanding.
The utility model content
The purpose of this utility model provides a kind of double side flexible copper coated board, can overcome three-layer process and make the problem that double side flexible copper coated board is difficult to the expensive and apparent difference of the deficiency of slimming and two-layer method flexibility coverlay, its excellent combination property, with low cost can be realized the slimming of base material.
According to above-mentioned purpose of the present utility model, a kind of double side flexible copper coated board is proposed, comprising: first Copper Foil, coat the polyimide layer on first Copper Foil, coat the adhesive layer on the polyimide layer and be overlaid on second Copper Foil on the adhesive layer.
Wherein, described first Copper Foil and second Copper Foil are electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m.
Described polyimide layer forms after by the polyamic acid imidization of coating on first Copper Foil, and thickness is 5-45 μ m.
The preferred 5-25 μ of the thickness of described polyimide layer m.
Described adhesive layer is modified epoxide resin adhesive or modified acrylic ester adhesion agent layer, and thickness is 6-35 μ m.
The gross thickness of double side flexible copper coated board is 14-50 μ m.
The beneficial effects of the utility model: have ultra-thin and circuit board gold and point unrippled characteristics, and have excellent folding resistance, thermal endurance, anti-flammability and good processing properties, also have advantage cheaply simultaneously, be convenient to produce in enormous quantities.
Description of drawings
Below in conjunction with accompanying drawing,, will make the technical solution of the utility model and other beneficial effects apparent by embodiment of the present utility model is described in detail.
In the accompanying drawing,
Fig. 1 is the schematic diagram of double side flexible copper coated board of the present utility model.
Embodiment
One, double side flexible copper coated board
As shown in Figure 1, double side flexible copper coated board 10 of the present utility model comprises: first Copper Foil 1, coat the polyimide layer 2 on first Copper Foil 1, coat the adhesive layer 3 on the polyimide layer 2 and be overlaid on second Copper Foil 4 on the adhesive layer 3.Wherein, described first Copper Foil 1 and second Copper Foil 4 are electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m; Described polyimide layer 2 forms after by the polyamic acid imidization of coating on first Copper Foil 1, and thickness is 5-45 μ m; The preferred 5-25 μ of the thickness of described polyimide layer 2 m; Described adhesive layer 3 is modified epoxide resin adhesive or modified acrylic ester adhesion agent layer, and thickness is 6-35 μ m; The gross thickness of prepared double side flexible copper coated board 10 is 14-50 μ m.
Two, the manufacture method of double side flexible copper coated board
1, the preparation of raw material
1.1,＜polyamic acid composition 〉
By tetracarboxylic acid anhydride compounds and diamine compounds be dissolved in DMAC or and nmp solvent in, in the proportion of the equivalent proportion 0.9-1.0 of acid anhydrides and amine, obtain polyamic acid solution 4-35 ℃ of following polymerization reaction.
1.2, modified epoxy resin composition
1.2.1 halogen-containing modified epoxy resin composition
Low bromine epoxy resin 10-40 weight portion;
High bromine epoxy resin 10-20 weight portion;
Nbr carboxyl terminal 15-30 weight portion;
Curing agent 5-15 weight portion;
Curing accelerator 0.05-1.5 weight portion;
Filler 20-100 weight portion;
Solvent: an amount of;
Above material mixing is evenly obtained modified epoxy resin composition.
1.2.2, the halogen modified epoxy resin composition
Phosphorous epoxy resin 30-60 weight portion;
End carboxylated nitrile rubber 15-30 weight portion;
Rubber modified epoxy resin 10-25 weight portion;
Curing agent 20-50 weight portion;
Curing accelerator 0.01-1.0 weight portion;
Antioxidant 0.01-1.0 weight portion;
Phosphonium flame retardant 5-30 weight portion;
Inorganic fire-retarded filler 0-100 weight portions;
Organic solvent is an amount of;
Above material mixing is evenly obtained modified epoxy resin composition.
1.3, acrylate modified resin combination
Acrylate copolymer 70-90 weight portion;
Epoxy resin 10-20 weight portion;
Curing accelerator 0.01-2 weight portion;
Other organic solvent of butanone or acetone is an amount of;
Above material mixing is evenly obtained the modified acrylic ester resin composition.
2, the making of flexibility coat copper plate
Above-mentioned composition is used for the preparation of two-sided Copper Foil flexibility coat copper plate by following technology.
Use coating equipment to be coated on first Copper Foil synthetic polyamic acid composition; drying through 80-200 ℃ of drying oven; remove DMAC and NMP organic solvent and dry compositions thus; by the high temperature oven that nitrogen protection is arranged the polyamic acid that is coated on first Copper Foil being carried out imidization under 330-380 ℃, obtain the single-sided polyimide flexibility coat copper plate after the cooling again.
Adopt the single-sided polyimide flexibility coat copper plate of above-mentioned gained, carry out corona treatment at its polyimide surface, with coating equipment synthetic modified epoxy resin composition or acrylic acid modified resin combination are coated on the surface treated polyimide surface, by traditional three-layer process flexibility coat copper plate manufacturing process, remove organic solvent through 80-170 ℃ of drying oven baking, make adhesive coating be in semi-cured state, under 60-100 ℃, carry out the compound double side flexible copper coated board that obtains with second Copper Foil then, progressively heating up under 80-170 ℃ makes adhesive layer finish curing again, obtains double side flexible copper coated board of the present utility model.
In the above-mentioned double side flexible copper coated board material, the dry thickness of polyimides membrane coat usually in the 5-45 mu m range, preferred 5-25 μ m; The thickness of above-mentioned used adhesive coating is 6-35 μ m; First Copper Foil and second Copper Foil can be rolled copper foil or electrolytic copper foil, and thickness is 9-70 μ m.
At making flexibility double face copper by said method and existing copper-clad plate compares, further give to illustrate in detail and describe as following embodiment.
The single-sided polyimide flexibility coat copper plate
(ODA) is dissolved in 1:1DMAC and nmp solvent with the diamines yl diphenyl ether; then under nitrogen protection; to be 0.998 BPDA anhydrides compounds such as (BPDA) with diamines yl diphenyl ether equivalent proportion, stir 8 hours down, and carry out polymerization reaction and obtain polyamic acid solution at 20 ℃.
Be coated in above-mentioned polyamic acid solution on the electrolytic copper foil of 18 μ m with coating equipment; thickness is 12 μ m; dried by the fire 3 minutes down at 160 ℃; be placed in then in the nitrogen protection baking oven, in 2 hours, temperature risen to 350 ℃, be incubated 5 minutes; be cooled to room temperature in 2 hours again; obtain the single-sided polyimide flexibility coat copper plate, handle with corona processor pair polyimide surface again, for future use.
The double-sided polyimide flexibility coat copper plate
Embodiment 1: modified epoxy resin composition
Low bromine epoxy resin (marque 530, DOW chemical company makes) 39 weight portions; Synthetic rubber (Zeon Corporation makes for marque Nipol 1072, acrylonitrile content 27 quality %) 20 weight portions; Diamino-diphenyl sulfone 2.5 weight portions; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.30 weight portion; Aluminium hydroxide (average grain diameter is 1 to 5 μ m, and purity is more than 99%) 30 weight portions; Antioxidant (marque 1010, CIBA GEIGY Co. makes) 0.20 weight portion.The solids content of regulating glue with butanone solvent is 40%, mixes and makes halogen-free epoxy resin composition.Be coated in said composition on the single-sided polyimide flexibility coat copper plate of above-mentioned processing by glue spreader, the coating adhesive layer thickness is 13 μ m, put in 160 ℃ the baking oven heat drying again into 3 minutes, then that itself and 18 μ m rolled copper foils is compound by roll-in, combined temp is 70 ℃, put 120-170 ℃ baking oven into and carry out the back by designing program and solidify being laminated with thing, make double side flexible copper coated board.
Embodiment 2: the halogen modified epoxy resin composition
Phosphorous epoxy resin (marque XZ92530, epoxide equivalent 340g/eq, phosphorus content 3.0 quality %, Dow Chemical Company makes) 38 weight portions; Synthetic rubber (Zeon Corporation makes for marque Nipol1072, acrylonitrile content 27 quality %) 20 weight portions; Rubber modified epoxy resin (CVC Specialty Chemicals Inc. makes for marque Hy RK84, elastomer content 32 quality %) 16 weight portions; Phosphorus containing phenolic resin (Dow ChemicalCompany makes for marque XZ92741, phosphorus content 9 quality %) 26 weight portions; Diamino-diphenyl sulfone 2.0 weight portions; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.30 weight portion; Aluminium hydroxide (average grain diameter is 1 to 5 μ m, and purity is more than 99%) 30 weight portions; Antioxidant (marque 1010, CIBA GEIGY Co. makes) 0.20 weight portion.The solids content of regulating glue with butanone solvent is 40%, mixes and makes halogen-free epoxy resin composition.Be coated in said composition on the single-sided polyimide flexibility coat copper plate of above-mentioned processing by glue spreader, coating adhesive thickness is 13 μ m, put in 160 ℃ the baking oven heat drying again into 3 minutes, then that itself and 18 μ m rolled copper foils is compound by roll-in, combined temp is 70 ℃, put 120-170 ℃ baking oven into and carry out the back by designing program and solidify being laminated with thing, make double side flexible copper coated board.
Acrylate copolymer (marque SG-70L, long rapids Co., Ltd.) 80 part, brominated bisphenol A epoxy resin (marque 530A80, DOW chemical company system) 25 part, curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.20 weight portion, (average grain diameter is 1 to 5 μ m to aluminium hydroxide, purity is more than 99%) 30 weight portions, antioxidant (marque 1010, CIBA GEIGY Co. makes) 0.20 weight portion, with butanone furnishing solids content is 40%, stirs to obtain the modified acrylic ester resin composition.Be coated in said composition on the single-sided polyimide flexibility coat copper plate of above-mentioned processing by glue spreader, coating adhesive thickness is 13 μ m, put in 160 ℃ the baking oven heat drying again into 3 minutes, then that itself and 18 μ m rolled copper foils is compound by roll-in, combined temp is 70 ℃, put 120-170 ℃ baking oven into and carry out the back by designing program and solidify being laminated with thing, make double side flexible copper coated board.
Comparative example 1: the science and technology marque SF302051513DRN250A of GUANGDONG SHENGYI three-layer process double side flexible copper coated board, the thick fire retarding epoxide resin glue-line of PI dielectric film 12.5 μ m/13 μ m/18 μ m rolled copper foils.
Comparative example 2: the compound polyimide glued membrane (PIXIO622) that Japanese clock deep pool 25 μ m are thick is compound under 350 ℃ with 18 μ m rolled copper foils, obtains not having glue double-sided polyimide flexibility coat copper plate.The performance that makes double side flexible copper coated board is referring to table 1.
Table 1
The method of testing of above characteristic is as follows:
Peel strength (PS) is tested the peel strength of metal cap rock according to IPC-TM-650 2.4.9 method.
Flammability (anti-flammability): measure according to UL94 vertical combustion method.
Anti-immersed solder is tested according to IPC-TM-650 2.4.13.
The etching ripple, with double face copper through big to respectively making the parallel circuit that the live width distance between centers of tracks is 3mm, observe basic unit and have or not corrugated.
Folding resistance carries out with reference to JIS C-6471, and test condition is 0.5Kg/0.8R, no coverlay.Whole etchings of Copper Foil of double sided board folding resistance, one side is done circuit and is tested.
Find out from above, flexibility coat copper plate of the present utility model, be etched into the fine rule road after base material do not have ripple, can do accurate circuit, and folding resistance has a circuit very good, can make full use of this advantage, improve the reliability of flex circuit application.
Above embodiment, be not that content to composition of the present utility model imposes any restrictions, every foundation technical spirit of the present utility model or composition composition or content all still belong in the scope of technical solutions of the utility model any trickle modification, equivalent variations and modification that above embodiment did.
Claims (6)
1, a kind of double side flexible copper coated board is characterized in that, comprising: first Copper Foil, be coated with the polyimide layer of being located on first Copper Foil, be coated with and be located at the adhesive layer on the polyimide layer and be overlaid on second Copper Foil on the adhesive layer.
2, double side flexible copper coated board as claimed in claim 1 is characterized in that, described first Copper Foil and second Copper Foil are electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m.
3, double side flexible copper coated board as claimed in claim 1 is characterized in that, described polyimide layer forms after by the polyamic acid imidization of coating on first Copper Foil, and thickness is 5-45 μ m.
4, double side flexible copper coated board as claimed in claim 3 is characterized in that, the preferred 5-25 μ of the thickness of described polyimide layer m.
5, double side flexible copper coated board as claimed in claim 1 is characterized in that, described adhesive layer is modified epoxide resin adhesive or modified acrylic ester adhesion agent layer, and thickness is 6-35 μ m.
6, double side flexible copper coated board as claimed in claim 1 is characterized in that, the gross thickness of described double side flexible copper coated board is 14-50 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNU2008202142149U CN201307967Y (en) | 2008-12-02 | 2008-12-02 | Double-sided flexible copper-clad plate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNU2008202142149U CN201307967Y (en) | 2008-12-02 | 2008-12-02 | Double-sided flexible copper-clad plate |
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| CN201307967Y true CN201307967Y (en) | 2009-09-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNU2008202142149U Expired - Lifetime CN201307967Y (en) | 2008-12-02 | 2008-12-02 | Double-sided flexible copper-clad plate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102448249A (en) * | 2010-10-15 | 2012-05-09 | 富葵精密组件(深圳)有限公司 | Method for manufacturing double-sided circuit board |
| CN102574364A (en) * | 2009-10-30 | 2012-07-11 | Jx日矿日石金属株式会社 | Method of manufacturing double-sided copper-clad laminate, and pair of copper or copper alloy foil sheets used thereupon |
-
2008
- 2008-12-02 CN CNU2008202142149U patent/CN201307967Y/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574364A (en) * | 2009-10-30 | 2012-07-11 | Jx日矿日石金属株式会社 | Method of manufacturing double-sided copper-clad laminate, and pair of copper or copper alloy foil sheets used thereupon |
| CN102574364B (en) * | 2009-10-30 | 2014-09-10 | Jx日矿日石金属株式会社 | Method of manufacturing double-sided copper-clad laminate, and pair of copper or copper alloy foil sheets used thereupon |
| CN102448249A (en) * | 2010-10-15 | 2012-05-09 | 富葵精密组件(深圳)有限公司 | Method for manufacturing double-sided circuit board |
| CN102448249B (en) * | 2010-10-15 | 2014-04-09 | 富葵精密组件(深圳)有限公司 | Method for manufacturing double-sided circuit board |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20090909 |